[go: up one dir, main page]

WO2003046653A1 - Electrolyte et dispositif electrochromique - Google Patents

Electrolyte et dispositif electrochromique Download PDF

Info

Publication number
WO2003046653A1
WO2003046653A1 PCT/JP2002/012444 JP0212444W WO03046653A1 WO 2003046653 A1 WO2003046653 A1 WO 2003046653A1 JP 0212444 W JP0212444 W JP 0212444W WO 03046653 A1 WO03046653 A1 WO 03046653A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
electrochromic
mass
compound
film
Prior art date
Application number
PCT/JP2002/012444
Other languages
English (en)
Japanese (ja)
Inventor
Shinji Ohshima
Masaki Minami
Junichiro Tanimoto
Takaya Kubo
Yoshinori Nishikitani
Original Assignee
Nippon Oil Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001364378A external-priority patent/JP2003161963A/ja
Priority claimed from JP2002080693A external-priority patent/JP4295466B2/ja
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Publication of WO2003046653A1 publication Critical patent/WO2003046653A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
    • G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
    • G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an electrolyte applicable to various electrochemical devices such as all-solid-state secondary batteries, wet-type solar cells, electric double-layer capacitors, electrolytic capacitors, and electrochromic devices at the electoral port.
  • the present invention relates to an electric-port chromic element useful for various uses such as a display element and light control glass.
  • Solid electrolytes such as a solid polymer electrolyte have been proposed as means for improving these disadvantages.
  • a solid polymer electrolyte using polyvinylidene fluoride has been proposed.
  • Japanese Unexamined Patent Publication (Kokai) No. Hei 8-5507407 discloses a lithium salt solution comprising a polyvinylidene fluoride-hexafluoropropylene copolymer and comprising a medium boiling point solvent in the film.
  • a solid electrolyte for a lithium-ion battery containing the same uniformly.
  • the polyvinylidene fluoride-hexafluoropropylene copolymer may contain a small amount of hydrogen fluoride depending on the production conditions, and this may cause a problem in the durability of the electrochemical element. Sometimes occurred.
  • a method for removing hydrogen fluoride contained in the copolymer polyvinylidene fluoride-hexafluoropropylene copolymer is dissolved in a good solvent such as DMF or acetone, and reprecipitated in a solvent such as water or alcohol.
  • a good solvent such as DMF or acetone
  • the solvent When applied to devices without removing a trace amount of hydrogen fluoride contained in the copolymer, the durability of various secondary batteries, wet solar cells, electric double-layer capacitors, electrolytic capacitors, electrochromic devices, etc. In an electrochemical device that requires, the solvent may be hydrolyzed, and it may be difficult to maintain the initial performance.
  • the present invention has been made in view of such circumstances, and has as its object to manufacture an electrochemical element by a simple method, to have high ionic conductivity, and to improve the durability of the element. To provide electrolytes that can be deployed in many applications.
  • electrochromic devices applied to various dimming devices and display devices.
  • a transparent conductive substrate an electoric chromic layer, an electrolyte, and a transparent conductive substrate (counter electrode) are sequentially arranged.
  • the configuration provided is a typical one.
  • the basic device performance is largely affected by the film physical properties of the electrochromic layer.
  • the elect port chromic layer the reduction coloring type elect port chromic case substances are used, oxidation evening tungsten (wo 3)
  • the film is typically deposited decoloring response of the elements, photochromic click properties , affected by the W 0 3 of film properties for performance such as durability.
  • W_ ⁇ 3 film a problem usually, a sputtering method, that can be produced by a vacuum deposition method such as electron beam vacuum deposition number, changes in membrane material properties by differences in environment and conditions at the time of vacuum deposition occurs There was a point.
  • the wo 3 film has a solid acid catalyzing ability. Therefore, there is a disadvantage that the constituent members of the electrolyte layer are deteriorated depending on the use conditions and the type of the electrolyte layer.
  • the present invention does not depend on the film physical properties of an electrochromic film by adding a specific basic substance to an electrolyte in an electrochromic element having an opening.
  • Ku thereby improving the device performance such as Chakushoiro response and durability can be suppressed element degradation by solid acid catalyzed even when using the W 0 3 layer as elect port electrochromic layer Elec Torokuromikku An element is provided.
  • the present inventors have made intensive studies to solve the conventional problems as described above, and as a result, have completed the present invention.
  • the present invention relates to an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound.
  • the present invention relates to an electrolyte comprising a supporting electrolyte, an organic solvent and a basic amine compound in a polymer matrix.
  • the polymer matrix is preferably a polyvinylidene fluoride-based polymer compound.
  • the basic amine compound is a tertiary amine.
  • the content of the basic amine compound is preferably 1 mass ppm to 1000 mass ppm with respect to the mass of the electrolyte.
  • the organic solvent is a solvent containing a phosphate compound or a phosphate compound.
  • the present invention is an electoric chromic element in which an electrolyte layer is sandwiched between two transparent conductive substrates, wherein at least one of the conductive substrates has an electrochromic layer. Further, the present invention relates to an electrochromic device, wherein the electrolyte contains a basic amine compound.
  • the basic amine compound is preferably a tertiary amine.
  • the electrolyte is preferably an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound.
  • the electrolyte may be a polymer matrix containing a supporting electrolyte, an organic solvent, and a basic amine compound. Preferably, it is quality.
  • the polymer matrix is preferably a polyvinylidene fluoride-based polymer compound.
  • the content of the basic amine compound is 1 mass ⁇ ! Preferably it is ⁇ 10000 mass ppm.
  • the organic solvent is a phosphate ester-based compound or a solvent containing a phosphate ester-based compound.
  • the electrochromic layer is made of tungsten oxide. Is preferred. Hereinafter, the present invention will be described in detail.
  • the present invention relates to an electrolyte containing a supporting electrolyte, an organic solvent, and a basic amine compound.
  • the present invention relates to an electrolyte comprising a supporting electrolyte, an organic solvent, and a basic amine compound in a polymer matrix.
  • a vinylidene fluoride polymer compound is preferably used as the polymer matrix.
  • salts, acids and alkalis usually used in the field of electrochemistry or batteries can be used.
  • the salt is not particularly limited, and examples thereof include inorganic ion salts such as alkali metal salts and alkaline earth metal salts, quaternary ammonium salts, cyclic quaternary ammonium salts, and quaternary phosphonium salts. Salts are preferred.
  • the salts include halogen ions, S CN @ -, C 10 4 one, BF 4 one, CF 3 S0 3 ⁇ (CF 3 S0 2) 2 N- ⁇ (C 2 F 5 S0 2) 2 N -, PF 6 -, AsF 6 - ⁇ CH 3 COO-, CH 3 (C fj H 4) S0 3 -, and (C 2 F 5 S0 2) L i salts with selection Bareru pair Anion from 3 C, Na salt, Alternatively, a K salt may be mentioned, and a Li salt is particularly preferred.
  • L i C10 4, L i S CN, L iBF 4, L i As F ri L i CF 3 S0 3, L iPF have L il, Na l, NaSCN, NaC 10 4, N aBF 4 , NaAs F 6 , KS CN, KC 1 and the like can be exemplified.
  • halogen ions SCN-, C 10 4 -, BF 4 -, CF 3 S0 3 - ⁇ (CF 3 S0 2) 2 N -, (C 2 F 5 S0 2) 2 N- ⁇ PF 6, A s F fi- , CH 3 C 00-, C
  • H 3 (C fi H,) S0 3 and (C 2 F 5 S0 2 ) 3 C— Phosphonium salts having, specifically, (CH 3 ) 4 PBF 4 , (C 2 H 5 ) 4 PBF 4 , (C 3 H 7 ) 4 PBF 4 , (C 4 H 9 ) 4 PBF 4 and the like.
  • Phosphonium salts having, specifically, (CH 3 ) 4 PBF 4 , (C 2 H 5 ) 4 PBF 4 , (C 3 H 7 ) 4 PBF 4 , (C 4 H 9 ) 4 PBF 4 and the like.
  • the acids are not particularly limited, and various inorganic and organic acids such as sulfuric acid, hydrochloric acid, phosphoric acids, sulfonic acids, and carboxylic acids can be used.
  • the alkalis are not particularly limited, and any of sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be used.
  • the amount of the supporting electrolyte used is arbitrary, but usually, it is preferably 0.01 M or more, preferably 0.05 M or more, more preferably 0.1 M or more in the organic solvent. On the other hand, it is usually 20 M or less, preferably 10 M or less, and more preferably 5 M or less.
  • the electrolyte generally contains 0.01% by mass or more, preferably 0.1% by mass or more, and usually 20% by mass or less, and preferably 10% by mass or less.
  • the organic solvent will be described.
  • any of the solvents generally used for electrochemical cells and batteries can be used.
  • phosphoric ester compounds acetic anhydride, methanol, ethanol, tetrahydrofuran, propylene carbonate, nitromethane, acetonitrile, dimethylformamide, dimethylsulfoxide, hexamethylphosphonamide, ethylene carbonate, dimethoxane, and acetonitrile Butyrolactone, avalerolactone, sulfolane, dimethyloxetane, propionitrile, glulononitrile, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolane, sulpholane, polyethylene Glycols and the like can be used.
  • phosphate ester compounds propylene carbonate, ethylene carbonate, Dimethylsulfoxide, dimethoxene, acetonitrile, abutyrolactone, Sulfolane, dioxolan, dimethylformamide, dimethoxetane, tetrahydrofuran, adiponitrile, methoxyacetonitrile, dimethylacetamide, methylpyrrolidinone, dimethylsulfoxide, dioxolan, sulfolane, trimethylphosphate, polyethylene glycol and the like are preferred.
  • the solvent one kind may be used alone, or two or more kinds may be used in combination.
  • a phosphoric ester compound or a solvent containing the phosphoric ester compound can also be used as a suitable compound.
  • the phosphate compound include trimethyl phosphate triethyl phosphate, tripropyl phosphate, ethyl dimethyl phosphate, triptyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, and phosphorus Examples thereof include trioctyl acid, trinonyl phosphate, tridecyl phosphate, tris (trifluoromethyl) phosphate, tris (pentafluoroethyl) phosphate, and triphenyl phosphate.
  • triethyl ester and trimethyl phosphate are preferable. preferable. Also, two or more of these can be used.
  • the amount of the solvent used is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more in the electrolyte, and the upper limit is usually 98% by mass, preferably 95% by mass. %, More preferably 90% by mass or less.
  • the basic amine compound used in the present invention functions as a proton acceptor in the electrolyte, and usually has a pKa of the conjugate acid in an aqueous solution at 25 ° C and an aqueous solution of 4 to 12, preferably 5 to 11. Those in the range can be mentioned.
  • Examples of such basic amine compounds include primary amines (RNH 2 ), secondary amines (: R 2 NH), tertiary amines (R 3 N) and derivatives thereof. it can.
  • polyamines such as diamine, triamine, and tetraamine can also be used.
  • R represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and may be the same or different.
  • Such a hydrocarbon group may be linear, branched, cyclic, saturated, or unsaturated, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an arylalkyl group, and an alkylaryl group. , Specifically, methyl, ethyl, propyl, butyl Group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, penzyl group, naphthyl group, etc. .
  • Specific compounds include, for example, triethylamine, trimethylamine, tripropylamine, triptylamine, trihexylamine, triphenylamine, getylamine, dimethylamine, dipropylamine, dibutylamine, dihexylamine, tetramethylethylenediamine, tetramethylbenzidine.
  • N N 'over diphenyl benzidine, Kishiruamin Jechiruamin, Jifue two Ruamin, Mechiruami down, Puropiruamin, butylamine, to di, Fueniruamin, 2 Nafuchiruamin, pyridine, 4, 4 5 - Bibirijiru, 2, 2, one Bibirijiru, 2 : 6-Lutidine, 3,4-lutidine, 4-dimethylaminopyridine, quinoline, 2-methylquinoline, isoquinoline, quinazoline, 1,3,5-triazine, 1,2,4-triazolate , Imidazole, aniline, N-methylaniline, N, N-dimethylaniline, 2,3-dimethylaniline, 2,6-dimethylaniline, pyrrole, carbazole, N-methylcarbazole, piperidine, 1-methylbiperidine , Piperazine, 1-methylbiperazine, 1,4-dimethylbiper
  • tertiary amines such as triethylamine, triphenylamine, pyridine, 4,4-bipyridyl, 2,6-lutidine and isoquinoline.
  • the amount of the basic amine compound is not particularly limited and may be appropriately selected, but is usually preferably 1 ppm by mass or more, more preferably 10 mass ppm or more, and particularly preferably, based on the total mass of the electrolyte. Is 50 mass ppm. On the other hand, it is preferably at most 10,000 mass ppm, more preferably at most 5,000 mass ppm, particularly preferably at most 1,000 mass ppm.
  • the electrolyte of the present invention ion conductivity, usually at room temperature 1 X 1 0- 7 S / cm or more, preferably 1 X 1 0 - 6 S / cm or more, more preferably 1 X 1 0 - 5 S / cm
  • Ionic conductivity can be determined by a general method such as the complex impedance method.
  • the polyvinylidene fluoride polymer compound preferably used as the polymer matrix in the present invention will be described.
  • Examples of the polyvinylidene fluoride-based high molecular compound used as the polymer matrix in the present invention include a homopolymer of vinylidene fluoride or a copolymer of vinylidene fluoride with another polymerizable monomer, preferably a radical polymerizable monomer. Copolymers are exemplified. Examples of other polymerizable monomers to be copolymerized with vinylidene fluoride (hereinafter, referred to as copolymerizable monomers) include hexafluoropropylene, tetrafluoroethylene, trifluoroethylene, ethylene, propylene, acrylonitrile. , Vinylidene chloride, methyl acrylate, ethyl acrylate, methyl methacrylate, styrene and the like.
  • copolymerizable monomers can be used in an amount of 1 to 100 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of vinylidene fluoride. Also, two or more of these copolymerizable monomers can be added. For example, copolymerization may be carried out using a combination of vinylidene fluoride + hexafluoropropylene + tetrafluoroethylene, vinylidene fluoride + tetrafluoroethylene + ethylene, vinylidene fluoride + tetrafluoroethylene + propylene, and the like.
  • Hexafluoropropylene is preferably used as the copolymerizable monomer.
  • a vinylidene fluoride-hexafluoropropylene copolymer obtained by copolymerizing 1 to 25% by mass of hexafluoropropylene with vinylidene fluoride is preferably used as a solid electrolyte having a high molecular matrix.
  • two or more kinds of vinylidene fluoride-hexafluoropropylene copolymers having different copolymerization ratios may be mixed and used.
  • these vinylidene fluoride-hexafluoropropylene copolymers are used during polymerization. Contains hydrogen fluoride due to decomposition of the monomer. Most of the hydrogen fluoride is removed by water washing, but remains in a trace amount, and is usually contained in an amount of about 10 to 100 ppm by mass, more typically on the order of tens of ppm.
  • one kind of a polymer compound selected from a polyacrylate-based polymer compound, a polyacrylonitrile-based polymer compound and a polyether-based polymer compound is used as the polymer matrix in the polyvinylidene fluoride-based polymer compound. It is also possible to use a mixture of two or more kinds.
  • the other polymer compound mixed with the polyvinylidene fluoride polymer compound is preferably 50% by mass or less.
  • the number average molecular weight of the polyvinylidene fluoride-based polymer compound used in the present invention is usually 10, 00 0 to 2, 0 0 0, 0 0 0, preferably 10 0, 0 0 0 Those having a range of 11, 0000, 0000 can be suitably used.
  • the above-mentioned various organic solvents can be combined as the organic solvent.
  • the phosphate ester compound or the phosphate ester compound A solvent containing is preferred.
  • the amount of the solvent used is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, and 80% by mass or less, preferably 70% by mass in the electrolyte. It is desirable to include the following amount.
  • Such a solid electrolyte can be easily obtained by forming a polyvinylidene fluoride polymer compound, a supporting electrolyte, an organic solvent, and a basic amine compound into a desired shape, for example, a sheet-to-film shape by a known method. I can do it.
  • the method in this case is not particularly limited, but a method obtained in a film state by a casting method can be preferably mentioned.
  • the film thickness can be adjusted by a coating apparatus, and it is usually preferable that the film thickness be 25 / m or more.
  • the upper limit of the film thickness is not particularly limited and may be arbitrarily selected. For example, when the film is manufactured by a casting method, the upper limit is usually about 500 m. The amount of the solvent in the solid electrolyte can be appropriately adjusted by selecting the drying conditions.
  • the shape and thickness of the solid electrolyte layer are appropriately selected depending on the application depending on the type of the device and are not particularly limited, but the thickness is usually lm or more. Preferably, it is particularly preferably at least 10 ⁇ m. On the other hand, it is preferably at most 3 mm, particularly preferably at most 1 mm.
  • the solid electrolyte of the present invention can be a stiff film, in which case its tensile modulus at 25 ° C. is preferably 5 ⁇ 10 4 N / m 2 or more.
  • the 1 X 1 0 5 N / m 2 or more, and most preferably it is desirable to have a characteristic is 5 X 1 0 5 N / m 2 or more.
  • the tensile modulus, tensile test machine generally used 2 cm X 5 by strip-shaped sample of cm is the value of the case having conducted the measurement c
  • the present invention is, two transparent conductive substrates An electrochromic element in which an electrolyte layer is sandwiched, wherein at least one of the conductive substrates has an electrochromic layer, and the electrolyte contains a basic amine compound.
  • the present invention relates to an electrochromic element.
  • the transparent conductive substrate means a transparent substrate that functions as an electrode.
  • the conductive substrate according to the present invention includes a substrate in which the substrate itself is made of a conductive material, and a laminate in which an electrode layer is laminated on one or both sides of a substrate having no conductivity. Regardless of whether or not it has conductivity, the substrate itself preferably has a smooth surface at room temperature, but that surface may be flat or curved, It may be deformed.
  • an electrochromic element in which both conductive substrates are transparent is suitable for a display element or light control glass.
  • the transparent conductive substrate is usually manufactured by laminating a transparent electrode layer on a transparent substrate.
  • transparent means having a light transmittance of 10 to 100% in the visible light region, and there may be a partially opaque portion.
  • the material of the transparent substrate is not particularly limited, and may be, for example, colorless or colored glass, reinforced glass, or the like, and may be colorless or colored transparent resin.
  • Specific examples of the transparent resin referred to here include polyethylene terephthalate, polyethylene naphtholate, polyamide, polysulfone, polyethersulfone, polyether-teretone, ketone, bolifenylene sulfide, polycarbonate, polyimide, Polymethyl methacrylate, polystyrene and the like.
  • the transparent electrode layer is not particularly limited as long as the object of the present invention is achieved, and examples thereof include a metal thin film such as gold, silver, chromium, copper, and tungsten, and a conductive film made of a metal oxide.
  • a metal thin film such as gold, silver, chromium, copper, and tungsten
  • a conductive film made of a metal oxide As the metal oxide, such as tin oxide, zinc oxide, and vanadium oxide, Indium Tin Oxide (IT 0 ( I n 2 0 3: S n)) doped with minor components thereto, Fluorine doped Tin Oxide (FTO ( Sn0 2: F)), Aluminum doped Zinc Oxide (AZ 0 (ZnO: a 1)) or the like is used as a preferable example.
  • the thickness of the electrode layer is usually 100 to 5000 ⁇ m, preferably 500 to 3000 ⁇ m.
  • the surface resistance (resistivity) is appropriately selected depending on the use of the substrate of the present invention
  • the method for forming the transparent electrode layer is not particularly limited, and a known method is appropriately selected and used depending on the type of the above-described metal or metal oxide used as the conductive layer. Usually, a vacuum evaporation method, an ion plating method, or the like is used. Method, CVD or sputter ring method, sol-gel method, etc. are used. In either case, it is desirable to form the substrate at a substrate temperature of 20 to 700 ° C.
  • the present invention is characterized in that at least one of the conductive substrates has an electrochromic layer.
  • the electrochromic layer is formed on a conductive substrate on a conductive substrate.
  • the material forming the electoric chromic layer may be any of an oxidative coloring type electrochromic compound and a reducing coloring type electrochromic compound.
  • Examples thereof include an inorganic compound of a metal oxide and various organic electrochromic compounds, and are not particularly limited.
  • an inorganic electochromic compound is preferable.
  • tungsten oxide (wo 3) vanadium oxide, molybdenum oxide, acid iridium, nickel oxide, titanium oxide, chromium oxide, manganese oxide, transition metal oxides and the ratio thereof of any such oxide cobalt
  • the oxide film included in the above is not particularly limited.
  • an inorganic electochromic compound is preferable.
  • tungsten oxide (wo 3) vanadium oxide, molybdenum oxide, acid iridium, nickel oxide, titanium oxide, chromium oxide, manganese oxide, transition metal oxides and the ratio thereof of any such oxide cobalt
  • a wet method such as a sol-gel method or an electrochemical method
  • a vacuum film forming method such as an evaporation method, a sputtering method, an ion plating method, or a pulse laser deposition method
  • a wet method such as a sol-gel method or an electrochemical method
  • a vacuum film forming method such as an evaporation method, a sputtering method, an ion plating method, or a pulse laser deposition method
  • the thickness of the chromic layer at the opening is not particularly limited, but is usually about 0.1 to 2 / m, preferably about 0.4 to 0.8 zm.
  • the electrochromic device of the present invention has an electrochromic layer on at least one side of the conductive substrate.
  • the transparent conductive substrate facing the conductive substrate having the electrochromic layer includes (a) In addition to the configuration using a conductive substrate, (b) a configuration using a conductive substrate having another electrification port chromic layer, and (c) a member in which conductive fine particles are bound on a conductive surface of the conductive substrate with a binder. May be arranged so that the light transmittance (or light reflectivity) required for the entire counter electrode is not impaired.
  • the form (c) is specifically described in, for example, Japanese Patent Application Laid-Open Nos. Hei 6-28190 and Hei 10-239719.
  • the electrochromic layer is disposed on both the conductive substrates, if one of the electrochromic layers is an oxidizing electrochromic layer, the other is a reducing electrochromic layer, and the other is an electrochromic layer.
  • the other is a reducing electrochromic layer at the opening, it is preferable to use an oxidizing electrochromic layer at the other side.
  • the electoric chromic layer of the other is not particularly limited, but may be nickel oxide, chromium oxide, or the like.
  • Preferred examples of the electrochromic device of the present invention include manganese oxide, cobalt oxide, iridium oxide, and Prussian blue.
  • Conductive fine particles with a binder It is preferable that a bound member is arranged.
  • Such conductive fine particles usually 10- 8 S ⁇ cm one 1 or more, preferably 10- 5 S - cm- 1 or more, more preferably Ru substance der showing a 10- 2 S ⁇ cm- 1 or more conductive It is desirable.
  • These conductive fine particles usually have an electric capacity of 1 farad / g or more, preferably 5 farads / g or more, more preferably 10 farads / g or more, or 1 clone / g or more. Preferably, it can store a charge amount of preferably 5 coulombs / g or more, more preferably 10 clones / g or more.c
  • a material constituting such fine particles for example, porous carbon
  • the fin evening one Kareshon material conductive fine particles having a 1 Fara' de / g or more electric capacity of the present invention that the conductive polymer compound, or mixtures thereof, if example embodiment, the surface area is typically, 10 m 2 / g or more, preferably 50 to 500 Om 2 / g, particularly preferably 300 to 4000 m 2 / g. Limit Those are in is not the name.
  • Such activated carbon can be obtained, for example, by a method of carbonization activation of palm, petroleum pitch,
  • Examples of the conductive fine particles capable of storing an electric charge of 1 clone / g or more according to the present invention include an in-situ radiation material, a conductive polymer compound, and the like. Materials that can be stored are preferred.
  • disulfides such as a known T i S 2, Mo S 2 ; C o 0 2, N i 0 dioxide such as 2; W 18 0 49, W 20 O 58 And the like.
  • examples of the conductive polymer compound include a conductive polymer compound containing polyalinine, polythiophene, polypropylene, polyphenylenevinylene, polyacene, or the like as a main component and obtained by doping or the like.
  • the particle size of the fine particles is not particularly limited as long as the object of the present invention is not impaired, but is usually 500 m to 0.1 m, preferably 200 m to 0.3 m, and more preferably 50 m.
  • An average particle size of Ml in the range of m to 0.5 m is preferred.
  • the electrolyte layer in the electorifice chromic element has an ion conductivity of 1 ⁇ 10 17 S / cm or more at room temperature, and plays a role of coloring, decoloring, and discoloring the electoral chromic layer.
  • Such an electrolyte layer can be formed using any of a liquid ion-conductive substance, a gelled liquid ion-conductive substance, and a solid ion-conductive substance. In particular, a solid ion-conductive substance is used. It is desirable.
  • Liquid ion conductive material Liquid ion conductive material
  • the liquid ionic conductive substance is prepared by dissolving a supporting electrolyte such as salts, acids and alkalis in a solvent.
  • any of the solvents generally used in electrochemical cells and batteries can be used, and specific examples include the organic solvents described above.
  • the use amount of the solvent is not particularly limited, but usually, the solvent accounts for at least 20% by mass, preferably at least 50% by mass, more preferably at least 70% by mass of the ion-conductive layer.
  • 9 8 wt%, preferably from 9 to 5% by weight, still as preferably c supporting electrolyte is 9 0 wt% or less, wherein the salts in the field of the field or the battery electrochemical Ru is typically used, acids, alkalis Can be used.
  • the supporting electrolyte may or may not be used, and when used, the amount of use is arbitrary.
  • the supporting electrolyte is usually 20 M or less in the ion conductive layer, preferably. Is preferably at most 10 M, more preferably at most 5 M, at least 0.1 M, preferably at least 0.05 M, even more preferably at least 0.1 M.
  • the gelled liquid-based ion-conductive substance means a substance obtained by thickening or gelling the above-mentioned liquid-based ion-conductive substance. This substance is obtained by adding a polymer or a gelling agent to the liquid-based ion-conductive substance. Is prepared.
  • the polymer used for this is not particularly limited, and examples thereof include polyacrylonitrile, carboxymethylcellulose, polyvinyl chloride, polyethylene oxide, Polyurethane, polyacrylate, polymethacrylate, polyamide, polyacrylamide, cellulose, polyester, polypropylene oxide, nafion and the like can be used.
  • the gelling agent is also not particularly limited, and oxyethylene methacrylate, oxyshethylene acrylate, urethane acrylate, acrylamide, agar, and the like can be used.
  • Solid ion conductive material
  • a solid ion-conductive substance refers to a substance that is solid at room temperature and has ion conductivity, including polyethylene oxide, a polymer of oxyethylene (meth) acrylate, naphion, polystyrene sulfonic acid, and polystyrene.
  • ether poly Ma one, full Uz Motokei polymers such Porifudzu fluoride polymer, Li 3 n, n a one ⁇ one A1 2 0 3, S n ( HP 0 4) the use of 2 ⁇ H 2 ⁇ like Can be.
  • a supporting electrolyte is dispersed in a polymer obtained by polymerizing an oxyalkylene methacrylate compound, an oxyalkylene acrylate 1, or a urea acrylate compound.
  • the solid polymer electrolyte molecular solid electrolyte can be used, the precursor ⁇ Les evening Nakurireto represented by the following general formula (1), the organic solvent, and a composition containing the supporting electrolyte And a solid polymer electrolyte obtained by solidifying this precursor.
  • R 1 and R 2 are the same or different groups and represent a group selected from the following general formulas (2) to (4).
  • R 3 and R 4 are the same or different groups, and represent a divalent hydrocarbon residue having 1 to 20, preferably 2 to 12 carbon atoms.
  • Y is a polyether unit (_ ⁇ —), a polyester unit (one C00—), polycarbonate Unit (-OCOO-) or a mixture of two or more of these units.
  • M represents an integer in the range of 1 to 100, preferably 1 to 50, and more preferably 1 to 20.
  • R 5 to R 7 are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 8 represents a divalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
  • 19 represents a trivalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
  • R 1. Represents a tetravalent organic residue having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms.
  • Examples of the divalent hydrocarbon residue represented by R 3 and R 4 in the general formula (1) include a linear divalent hydrocarbon group, an aromatic hydrocarbon group, and an alicyclic hydrocarbon group.
  • the molecular weight of the urethane acrylate represented by the general formula (1) is not particularly limited, but is preferably 2,500 to 30,000, more preferably 3,000 to 20,000.
  • the amount of the organic solvent to be added is usually 100 to 1200 parts by mass, preferably 200 to 900 parts by mass, based on 100 parts by mass of the urethane acrylate. If the added amount of the organic solvent is too small, the ionic conductivity is not sufficient, and if the added amount of the organic solvent is too large, the mechanical strength may be reduced.
  • the supporting electrolyte is appropriately selected depending on the use, etc.
  • the amount of addition is 0.1 to organic solvent. It is 30% by mass, preferably 1 to 20% by mass.
  • Such optional components include, for example, a crosslinking agent, a polymerization initiator (light or heat), an ultraviolet absorber, and the like.
  • a composition comprising a monofunctional acryloyl-modified polyalkylene oxide represented by the following general formula (5), a polyfunctional acryloyl-modified polyalkylene oxide, the organic solvent, and the supporting electrolyte And a solid polymer electrolyte obtained by solidifying the precursor.
  • I 11 , R 12 , R 13 and R 14 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, which may be the same or different, and R 11 is a hydrogen atom, a methyl group; R 12 is a hydrogen atom, a methyl group, R 13 is a hydrogen atom, a methyl group, and R 14 is a hydrogen atom, a methyl group, or an ethyl group.
  • n represents an integer of 1 or more, preferably 1 to 100, more preferably 2 to 50, and further preferably 2 to 30.
  • the oxyalkylene units may have different so-called copolymerized oxyalkylene units.
  • polyfunctional acryloyl-modified polyalkylene oxide used in the present invention include a compound represented by the general formula (6), a so-called bifunctional acryloyl-modified polyalkylene oxide, and a compound represented by the general formula (7). And the so-called polyfunctional acryloyl-modified polyalkylene oxide having three or more functional groups.
  • R 15 , R 16 , R 17 and R 18 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and p represents an integer of 1 or more.
  • R ig , R 2 ° and R 21 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, q represents an integer of 1 or more, and r represents 2 to Is an integer of 4, and L represents an r-valent linking group.
  • the linking group L is usually a divalent, trivalent or tetravalent hydrocarbon group having 1 to 30, preferably 1 to 20 carbon atoms.
  • a bifunctional acryloyl-modified polyalkylene oxide represented by the general formula (6) and a trifunctional or higher polyfunctional acryloyl-modified polyalkylene oxide represented by the general formula (7) may be used in combination.
  • the mass ratio is usually 0.1 to 99.9-99.9 / 0.1, preferably 1/1.
  • a range of 99 to 99/1, more preferably 20/80 to 80/20 is desirable.
  • the mass ratio of the compound represented by the general formula (5) to the polyfunctional acryloyl-modified polyalkylene oxide used in the present invention is usually 1 / ⁇ .001 to; L / l, preferably 1 / 0.05 to 1 /. It is in the range of 0.5.
  • the compounding ratio of the organic solvent is usually in the range of 50 to 800% by mass, preferably 100 to 500% by mass with respect to the total mass of the compound represented by the general formula (5) and the polyfunctional acryloyl-modified polyalkylene oxide. Is desirable.
  • the compounding ratio of the supporting electrolyte is usually 1 to 30% by mass, preferably 3 to 20% by mass based on the total mass of the compound represented by the general formula (5), the polyfunctional acryloyl-modified polyalkylene oxide and the organic solvent. % Range.
  • ком ⁇ онент can be added as needed, as long as the object of the present invention is not impaired.
  • optional components include, but are not particularly limited to, a photopolymerization initiator for photopolymerization, a thermal polymerization initiator for thermal polymerization, and an ultraviolet absorber.
  • the amount of the polymerization initiator to be used is usually 0.005 to 0.005 mass of the compound represented by the general formula (5) and the polyfunctional acryloyl-modified polyalkylene oxide. It is in the range of 5% by weight, preferably 0.01 to 3% by weight.
  • the polymer solid electrolyte As a third example of the polymer solid electrolyte, a composition containing the organic solvent and the supporting electrolyte in a polymer matrix composed of a polyvinylidene fluoride-based polymer compound is used as a precursor. And the solid polymer electrolyte obtained by solidifying the polymer.
  • the thickness of the ion conductive layer is not particularly limited, but is usually 20 / ⁇ ! ⁇ ⁇ 1 mm, preferably in the range of 50-500 ⁇ m.
  • the present invention is characterized in that the ion conductive layer contains a basic amine compound.
  • the basic amine compound the above-described basic amine compounds can be used.
  • the amount of the basic amine compound is 1 mass ⁇ ⁇ ⁇ ! 1100000 mass ppm. It is preferably from 10 to 500 mass ppm, particularly preferably from 50 to: L000 mass ppm.
  • FIG. 1 As an example of the electrochromic device of the present invention, an example shown in FIG. 1 can be given. This device has a stripe member 1 1 in which a transparent conductive film 32 on a transparent substrate 31 and conductive fine particles formed on the transparent conductive film 32 are bound with a binder.
  • a color electrode formed by forming a transparent color conductive film 36 on a transparent substrate 37 and a reduction color (or oxidation color) electoral port chromic film 35 is formed. Is formed. The gap between the two is filled with an electrolyte 34, the periphery is sealed with a sealing material 38, and the transparent conductive film (32, 36) is connected to a power supply 39 via a lead wire via a bus 40. Have been.
  • the method of making the electrochromic color-forming electrode on which the electrochromic film is disposed and the counter electrode facing each other and the method of arranging the busper are not particularly limited. Various methods are possible depending on the form.
  • the electrolyte of the present invention can be used as an electrolyte for electrochemical devices such as all-solid-state secondary batteries, wet solar cells, electric double-layer capacitors, electrolytic capacitors, and electrochromic devices.
  • electrochemical devices such as all-solid-state secondary batteries, wet solar cells, electric double-layer capacitors, electrolytic capacitors, and electrochromic devices.
  • the improved adhesion to the electrodes and the high ionic conductivity, mechanical strength, and stability over time make it possible to easily manufacture higher-performance electrochemical devices.
  • It can be suitably used as an electrolyte for secondary batteries, high-energy batteries, and the like. Even when used in electrochemical devices, it has features such as no problems such as liquid leakage and excellent flame retardancy and durability.
  • the electroporous chromic element of the present invention can significantly improve the durability of the electrochromic element by including a predetermined amount of a basic amine compound in the electrolyte layer. It was possible to suppress a decrease in transparency of the chromic element during use over time.
  • the electoric chromic element of the present invention since it is not affected by the film physical properties of the electoral chromic layer, it is possible to suppress a change in the color responsiveness in the heat resistance test. Therefore, the electoric chromic element of the present invention is required to have durability. It can be used for various purposes such as windows and partitions of buildings and vehicles, various dimming devices, and furthermore, for example, character display devices, anti-glare mirrors, and decorative devices.
  • Example 1 Example 1
  • Poly (hexa fluoroalkyl propylene to vinylidene fluoride I) (trade name: Atofuina 'Japan Ltd. K YNAR 275 1) 2 g, pyridine 50 mg and L i BF 4 0. 3 g: the, Toryechiru phosphate 2 g and Aseton 6 g) to obtain a uniform solution, and after cooling to room temperature, apply it on a glass substrate by a dough-blade method, then heat and dry to evaporate the acetone in the solution, and make it 200 ⁇ m thick. A film-like solid electrolyte was obtained.
  • the solid electrolyte is easily peeled off from the glass substrate, it can be handled, the tensile elastic modulus was 3 X 10 ⁇ ⁇ / ⁇ 2 .
  • the solid electrolyte was measured ionic conductivity at complex Inpidansu method to obtain a good value of 1 X 10- 4 SZ cm.
  • LiTFS I lithium trifluoromethanesulfonimid
  • This solid electrolyte was easily separated from the glass substrate and could be handled, and the tensile elastic modulus was 4 ⁇ 10 6 N / m 2 .
  • solid electrolyte was obtained by complex Inpi one dance method Ion conductivity measured Toko filtration, good numerical values of 2 X 10- 4 SZcm.
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1.
  • Example 3
  • Poly (vinylidene fluoride-hexafluoropropylene) (trade name: Atofina-Japan, mixture of KYNAR2751 and 2801, mixing ratio 1: 1) 2 g, isoquinoline 5 Omg and LiTFS I 0.5 g, phosphorus Heat and dissolve in 8 g of Triethyl acid to obtain a uniform solution, cool to room temperature, apply it on a glass substrate by the doctor blade method, and then heat and dry to evaporate the Triethyl phosphate in the solution. A film-like solid electrolyte having a uniform thickness was obtained.
  • This solid electrolyte was easily peeled off from the glass substrate and could be handled, and the tensile elastic modulus was 3 ⁇ 10 fiN / m 2 .
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1.
  • Example 4
  • the solid electrolyte was measured Ion conductivity at complex impedance method, to obtain a good value of 1 X 10- 4 SZ cm.
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1.
  • Example 5
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1.
  • Example 6
  • the solid electrolyte was measured Ion conductivity at complex impedance method, to obtain a good value of 1 X 10- 4 S / cm.
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1.
  • Poly (vinylidene fluoride hexafluoropropylene) (trade name: Atofina-Japan KYNAR275 1) 2 g, isoquinoline 50 mg and LiBF 4 0.3 g was heated and dissolved in a mixed solution of triethyl phosphate 8 g and propylene carbonate 3 g to obtain a uniform solution.After cooling to room temperature, the solution was coated on a glass substrate by the doctor blade method, and then heated and dried. Then, 50% by mass of the mixed solvent was evaporated to obtain a uniform solid electrolyte in the form of a film having a thickness of 200 / m. This solid electrolyte was easily peeled off from the glass substrate and could be handled. The tensile modulus was 3 ⁇ 10 6 N / m 2 , confirming that the solid electrolyte was self-supporting.
  • the solid electrolyte was measured Ion conductivity at complex impedance method, 3 X 1 0 - obtain a good value of 4 S / cm.
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. It is clear that this solid electrolyte is also excellent in durability as in Example 1. Comparative Example 1
  • the solid electrolyte was measured Ion conductivity at complex impedance method, to obtain a good value of 1 X 1 0- 4 S / cm .
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. As is clear from Table 1, the amount of the hydrolyzate of the solvent contained in the film-shaped solid electrolyte of Comparative Example 1 was large, and the durability was lower than that of Example 1. Comparative Example 2
  • Table 1 also shows the results of the same durability test as in Example 1 for this film-shaped solid electrolyte. As is clear from Table 1, the amount of the hydrolyzate of the solvent contained in the film-form solid electrolyte of Comparative Example 1 was large, and the durability was inferior to that of Example 1. table 1
  • Tungsten oxide was evaporated to a thickness of 500 nm on 1TO glass of 10 cm ⁇ 100111 to produce an elect-opening chromic electrode.
  • Activated carbon powder product name “YP17”, manufactured by Kuraray Co., Ltd., surface area: 1500 m 2 / g) 8 g
  • Graphite product name “USSP”, manufactured by Nippon Graphite Trading Co., Ltd.
  • Recon varnish trade name “7931”, manufactured by Okitsumo Co., Ltd. 2 25 g of butyl cellosolve was added to 6.7 g and mixed to prepare an activated carbon paste.
  • the activated carbon paste was printed as a stripe member on a lO cmx l O cm ITO glass using a screen equidistantly arranged so that the stripe member of 0 ⁇ m was 20% of the total area. Then, it was heat-cured at 180 ° C. for 90 minutes to prepare a counter electrode.
  • the chromic electrode of the electoral opening was opposed to the counter electrode substrate at an interval of 0.3 mm, and the periphery was sealed with epoxy resin.
  • the electrolyte was vacuum injected into the inside, and the injection port was sealed with epoxy resin.
  • a lead wire was connected to each of the electrochromic electrode and the counter electrode substrate to prepare a device. The performance evaluation of the obtained device was evaluated based on the following test.
  • Tv luminous transmittance
  • a luminosity transmittance meter MODEL 304 manufactured by Asahi Spectroscopy.
  • a current of 20 mA regulated voltage: 1.5 V
  • Tv reached 20% the mode was switched to the decoloring mode, and a current of 20 mA (regulated voltage: 1.0 V) was applied so that the chromic electrode on the electoral port was positive and the opposite electrode was negative.
  • the electrochromic device was left at 80 ° C. for 1,000 hours, but the transparency of the device was not changed.
  • the color erasing response was not changed at all.
  • Tungsten oxide was vapor-deposited on a 10 cm ⁇ 10 cm ITO glass to a thickness of 500 nm to fabricate an electoc-chromic electrode.
  • Activated carbon powder (trade name “YP 17”, manufactured by Kuraray Co., Ltd., surface area 150 OmVg) 8 g
  • Graphite (trade name “US SP”, manufactured by Nippon Graphite Shoji Co., Ltd.) 4 g
  • Activated carbon paste was prepared by adding and mixing 25 g of butylcellosolve to 26.7 g. Then, a stripe member with a stripe width of 500 m and a height of 100 m comprised 20% of the total area. Using a screen placed at equal intervals so as to obtain the above, the above-mentioned activated carbon paste was printed as a stripe member on a 10 cm x 10 cm IT0 glass, and then heat-hardened at 180 ° C for 90 minutes. A counter electrode was produced.
  • O main butoxy polyethylene glycol monomethyl drink evening acrylate (Shin-Nakamura Chemical Co. Stock Company M 40 GN [Number of oxyethylene units 4]) 1.0 g, Polyethylene glycol dimethyl acrylate (Shin-Nakamura Chemical Co., Ltd.
  • the electrochromic coloring electrode was opposed to the counter electrode substrate at a distance of 0.3 mm, and the periphery was sealed with an epoxy resin.
  • the electrolyte was vacuum-injected into the inside, the inlet was sealed with epoxy resin, and the electrolyte was gelled by irradiating with a fluorescent lamp overnight.
  • a lead wire was connected to each of the electorifice chromic electrode and that of the counter electrode substrate, thereby producing a device. The performance of the obtained device was evaluated based on the following test.
  • Tv luminous transmittance
  • Oxidized tungsten was vapor-deposited to a thickness of 500 nm on I O cmx I O cm I T0 glass to produce an electrochromic coloring electrode.
  • an iridium oxide was deposited to a thickness of 5000 A to produce a counter electrode substrate.
  • the electrochromic coloring electrode and the counter electrode substrate were opposed to each other at a distance of 0.3 mm, and the periphery was sealed with an epoxy resin.
  • the electrolyte was vacuum-injected into the inside, the inlet was sealed with epoxy resin, and the electrolyte was gelled by irradiating with a fluorescent lamp overnight.
  • a lead wire was connected to each of the electrochromic electrode and the counter electrode substrate to prepare a device. The performance of the obtained device was evaluated based on the following test.
  • Tv luminous transmittance
  • Oxidized tungsten was vapor-deposited on 10 cm ⁇ 100111 1TO glass to a thickness of 500 nm to produce an elect-port chromic color electrode.
  • Activated carbon powder (trade name “YP 17”, manufactured by Kuraray Co., Ltd., surface area 150 OmVg) 8 g
  • graphite (trade name “USSP”, manufactured by Nippon Graphite Shoji Co., Ltd.) 4 g
  • Activated carbon paste was prepared by adding and mixing 25 g of butyl cellosolve to 26.7 g, and then the stripe member with a stripe width of 500 im and a height of 100 m was made up to 20% of the total area.
  • the above-mentioned activated carbon paste was printed as a stripe member on I O cm x I O cm ITO glass, and then heat-hardened at 180 ° C for 90 minutes, and the counter electrode was Produced.
  • the electrochromic coloring electrode and the counter electrode substrate were opposed to each other at a distance of 0.3 mm, and the periphery was sealed with an epoxy resin.
  • the electrolyte was vacuum injected into the inside, and the injection port was sealed with epoxy resin.
  • a lead wire was connected to each of the electorifice chromic electrode and the counter electrode substrate to prepare a device. The performance evaluation of the obtained device was evaluated based on the following test.
  • Tv luminous transmittance
  • FIG. 1 is a cross-sectional view showing one embodiment of the electrochromic device of the present invention.
  • FIG. 2 is an example of a front view of a counter electrode.
  • FIG. 3 is an example of a front view of the counter electrode.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne un électrolyte permettant de fabriquer par un procédé simple un dispositif électrochromique qui présente une conductivité ionique élevée, n'engendre pas de problèmes tels qu'une fuite de liquide, possède d'excellentes propriétés ignifuges et de transparence, et peut être utilisé dans diverses applications ; ce dispositif contient un électrolyte support, un solvant organique et un composé d'amine basique. Le dispositif électrochromique comporte deux substrats conducteurs transparents entre lesquels se situe une couche électrochromique ; une couche électrochromique est appliquée à au moins un des deux substrats transparents, et la couche d'électrolyte contient un composé d'amine basique. Les performances du dispositif telles que réaction de coloration/décoloration et durabilité, sont améliorées quelles que soient les propriétés physiques de la couche électrochromique.
PCT/JP2002/012444 2001-11-29 2002-11-28 Electrolyte et dispositif electrochromique WO2003046653A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001364378A JP2003161963A (ja) 2001-11-29 2001-11-29 エレクトロクロミック素子
JP2001-364378 2001-11-29
JP2002-080693 2002-03-22
JP2002080693A JP4295466B2 (ja) 2002-03-22 2002-03-22 固体電解質

Publications (1)

Publication Number Publication Date
WO2003046653A1 true WO2003046653A1 (fr) 2003-06-05

Family

ID=26624763

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/012444 WO2003046653A1 (fr) 2001-11-29 2002-11-28 Electrolyte et dispositif electrochromique

Country Status (1)

Country Link
WO (1) WO2003046653A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7630117B2 (en) 2004-09-21 2009-12-08 Lg Chem, Ltd. Electrolyte comprising eutectic mixture and electrochromic device using the same
CN114296285A (zh) * 2021-12-16 2022-04-08 烟台大学 一种用于普鲁士蓝基电致变色器件的高性能电解质

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5673423A (en) * 1979-11-21 1981-06-18 Elna Co Ltd Electrolyte for driving electrolytic condenser
JPH0215567A (ja) * 1988-07-01 1990-01-19 Sanyo Electric Co Ltd 非水系電解液電池
JPH0343960A (ja) * 1989-07-11 1991-02-25 Sanyo Electric Co Ltd 非水電解液電池

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5673423A (en) * 1979-11-21 1981-06-18 Elna Co Ltd Electrolyte for driving electrolytic condenser
JPH0215567A (ja) * 1988-07-01 1990-01-19 Sanyo Electric Co Ltd 非水系電解液電池
JPH0343960A (ja) * 1989-07-11 1991-02-25 Sanyo Electric Co Ltd 非水電解液電池

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7630117B2 (en) 2004-09-21 2009-12-08 Lg Chem, Ltd. Electrolyte comprising eutectic mixture and electrochromic device using the same
CN114296285A (zh) * 2021-12-16 2022-04-08 烟台大学 一种用于普鲁士蓝基电致变色器件的高性能电解质

Similar Documents

Publication Publication Date Title
EP0519921B1 (fr) Elément électrochromique, matériaux utilisés dans un tel élément, procédé de production d'un tel élément et de tels matériaux et utilisation d'un tel élément dans un dispositif électrochromique
KR101731301B1 (ko) 다공성 고분자막을 이용한 전기변색소자 및 이를 포함하는 스마트 창호
JP6256841B2 (ja) 可撓性透明エレクトロクロミック素子およびその調製のための方法
US11203688B2 (en) Composite containing organic/metallic hybrid polymer and ionic liquid, electrochromic device in which same is used, and method for manufacturing said composite and device
JP2014510944A (ja) 安定したエレクトロクロミックモジュール
CN104049432A (zh) 电致变色显示元件和显示器件
Ganesh et al. Designing an all‐solid‐state tungsten oxide based electrochromic switch with a superior cycling efficiency
KR20200038456A (ko) 투명한 이온 교환 멤브레인을 갖는 전기 광학 장치
JP4360663B2 (ja) エレクトロクロミックミラー
Wu et al. Electrochromic materials: Scope for the cyclic decay mechanisms and performance stability optimisation strategies
EP3444663B1 (fr) Dispositif électrochromique et son procédé de fabrication
KR102052440B1 (ko) 전기 변색성 슈퍼 커패시터
JPH11183942A (ja) エレクトロクロミック素子
JP2003161963A (ja) エレクトロクロミック素子
WO2003046653A1 (fr) Electrolyte et dispositif electrochromique
KR101780704B1 (ko) 겔 폴리머 전해질 조성물 및 이를 이용한 전기 변색 소자
JP2003043526A (ja) エレクトロクロミック素子
JPH04328723A (ja) エレクトロクロミック素子
JP2003015164A (ja) エレクトロクロミック素子
WO2003003110A1 (fr) Element electrochromique
JP2004101729A (ja) 薄膜
WO1999032928A1 (fr) Element electrochromique
JP2006134827A (ja) 電極および色素増感型太陽電池
JPH06242474A (ja) エレクトロクロミック素子及び高分子電解質薄膜の製造方法
RU2676807C2 (ru) Электрохромное устройство и способ его изготовления

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): DE FR GB

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase